1. Field of the Invention
The present invention relates to a treatment for making a heat exchanger, especially, a car evaporator which is used in air conditioners such as those for vehicles, hydrophilic, more specifically, a treatment method for making a heat exchanger with an excellent lasting hydrophilicity, deodorizing capability and corrosion resistance hydrophilic, and a heat exchanger treated to be hydrophilic by said method (hydrophilic heat exchanger).
2. Background Art
In general, heat exchangers are constructed of aluminum, and complex in structure having aluminum fins for the heat exchange held between pipes within narrow spaces. Therefore, it has been devised so as to facilitate the discharge of condensed water during the cooling operation by making the surface of aluminum fins, etc. hydrophilic. However, since the surface of aluminum fins, etc, which has been made hydrophilic as described above, is exposed to severe conditions including the repeated cycle of xe2x80x9cheating←xe2x86x92coolingxe2x80x9d, and adhesion of condensed water, atmospheric dusts or microorganisms, there have been problems that it is difficult to maintain the hydrophilicity of the surface of heat exchanger for a long period.
A variety of inventions have been made to solve these problems, and, for example, in Japanese Patent Laid-open Publication No. Hei 5-202313, a treatment agent for hydrophilicity comprising a mixture of polyvinyl alcohol and water-dispersible silica or a complex thereof, and lithium metasilicate has been disclosed. Herein, lithium metasilicate is said to be effective in maintaining the lasting hydrophilicity, lowering the freezing temperature and expressing antimicrobial activity.
In addition, in Japanese Patent Laid-open Publication No. Hei 5-214273, a paint composition consisting of a water-soluble or water-dispersible organic resin, nitrogen-containing anticorrosive and silica particulates, and coated aluminum materials with coating film obtained from this paint composition have been disclosed.
Furthermore, in Japanese Patent Publication No. 2649297, a paint composition for fin materials made of aluminum or aluminum alloy containing water-soluble or water-dispersible organic resin (excluding water-soluble amino resins), water-soluble amino resin, water-dispersed agglutinating colloidal silica containing silanol groups of 50 mxcexcxcx9c2 mxcexc in particle size, or water-dispersible humed silica powder, and a surfactant with HLB value of 8xcx9c18, fin materials and a method for manufacturing these fin materials have been disclosed. This invention aims at obtaining a pre-coated type fin material and a hydrophilic coating resistant to drawless processing (ironing) during the manufacturing of heat exchanger.
In addition, in Japanese Patent Laid-open Publication No. Hei 10-30069, an aqueous agent to give hydrophilicity containing colloidal silica of 5xcx9c100 nm in dispersed particle size and carboxylic acid polymer at pH 1xcx9c5, and a method for manufacturing pre-coated fin materials for the heat exchanger using this agent have been disclosed.
All of these aforementioned prior arts have aimed to enhance the hydrophylicity of paint compositions utilizing irregularities of silica surface by using water-soluble or water-dispersible resin together with colloidal silica or particulate silica. However, hydrophilic coatings formed by the combined use of resin and particulate silica tend to deteriorate due to the long time use of heat exchanger. As a result, particulate silica is exposed, posing problems such as emission of silica specific dust smell or stink from materials adsorbed on silica.
Furthermore, fins, etc. of heat exchanger are often assembled (constructed) by brazing using solders such as aluminum-silicon alloy, aluminum-silicon-magnesium alloy, etc. However, deposits from solders adhering to the surface of fins, etc. during brazing often lead to difficulties in rust preventive treatment such as chemical transformation, posing problems such as the decrease in the corrosion resistance of heat exchanger and formation of white rust. Furthermore, there have been other problems that molds growing in water adsorbed to white rust are strewn inside buildings and automobiles by the ventilator fan, generating stink.
The aforementioned problems maybe solved if deposits from solders can be cleaned off by the pretreatment such as washing, it was difficult however to sufficiently clean away said deposits by the conventional washing with acid, alkali or surfactant. For example, in Japanese Patent Laid-open Publication No. Hei 11-131254, a method for treating the surface of aluminum-containing metal materials has been disclosed, wherein the chemical etching treatment of metal materials is performed, prior to the treatment to make the surface hydrophilic, using an acidic aqueous solution containing at least one acid selected from a group consisting of sulfuric acid, hydrofluoric acid, nitric acid and phosphoric acid, and then the chemical transformation technique was applied to the etched surface with the aqueous solution of ziruconium (Zr) phosphate or titanium (Ti) phosphate. However, the aforementioned prior art was not sufficiently effective in removing said deposits, and aluminum-containing metal materials subjected to the treatment to make them hydrophilic still had a tendency to develop white rust in a prolonged salt water spraying test.
In view of the aforementioned problems, the present invention has been made, aiming to provide a treatment method for making a heat exchanger hydrophilic, which is superb in the lasting hydrophilicity, deodorizing capability and corrosion resistance, and a heat exchanger thus treated for making it hydrophilic (hydrophilic heat exchanger).
To achieve the aforementioned purposes, a treatment method of this invention for making the metal surface hydrophilic aims to sufficiently clean off deposits of solders by devising a pickling agent for the cleaning process performed prior to the chemical transformation treatment, facilitating the subsequent chemical transformation treatment. With such a treatment method, it has become possible for the first time to improve the corrosion resistance of heat exchanger and at the same time prevent the stink emission caused by white rust.
In addition, a treatment method for hydrophilicity of this invention is to enhance the lasting hydrophilicity and deodorizing capability of the heat exchanger by using a treatment for making the metal surface hydrophilic comprising silica particulates coated with polymer of vinyl alcohol series dispersed in aqueous medium.
Specifically, this invention provides the following cleaners and cleaning methods.
(1) A pickling method for a heat exchanger made of aluminum materials, wherein a cleaning treatment is performed by bringing said heat exchanger into contact with a pickling agent containing at least one acid selected from a group comprising nitric acid, sulfuric acid and hydrofluoric acid prior to the chemical transformation treatment applied to said heat exchanger.
As the example of a pickling agent used in this invention, there are aqueous solutions comprising nitric acid, sulfuric acid or hydrofluoric acid, or combinations thereof, and further supplemented with iron salts. The acid concentration of these cleaners is preferably 1xcx9c10 N, more preferably 3xcx9c5 N.
(2) The pickling method according to the aforementioned (1), wherein said pickling agent contains an iron salt.
(3) The pickling method according to the aforementioned (2), wherein said iron salt is iron sulfate, iron nitrate, iron acetate or iron chloride.
(4) The pickling method according to the aforementioned (2) or (3), wherein said pickling agent contains an iron salt in the range 0.01xcx9c5 weight percent.
Said pickling agents preferably contain iron salts such as iron sulfate, iron nitrate, iron acetate, iron chloride, etc. Said iron salts are contained favorably at 0.01xcx9c5 weight percent in an acidic aqueous solution, more preferably made to contain at 0.1xcx9c1 weight percent. It is advantageous that iron salts contained in the aforementioned concentration range contribute to a more effective acidic washing off of deposits caused by solders. Pickling agents containing iron salts can be preferably used in the case of the formation of chemical conversion coating film of zirconium series with a slightly inferior corrosion resistance in particular.
(5) The pickling method according to the aforementioned (4), wherein said cleaning treatment comprises bringing said heat exchanger into contact with said pickling agent under the conditions at 10xcx9c70xc2x0 C. for 30 sxcx9c5 min.
Conditions for cleaning treatment are preferably at 10xcx9c85xc2x0 C. for the liquid temperature of cleaners and for 30 sxcx9c5 min as the contact time. When the liquid temperature is lower than 10xc2x0 C. or the contact time is less than 30 s, removal of deposits, etc. may become insufficient, and when the temperature exceeds 85xc2x0 C., or the contact time is longer than 5 min, etching (cleaning treatment) may become excessive.
(6) The pickling method according to any of the aforementioned (1)xcx9c(5), wherein said heat exchanger has brazed parts.
(7) The pickling method according to any of the aforementioned (1)xcx9c(6), wherein said heat exchanger is a car evaporator.
A pickling method according to this invention can be preferably used for heat exchangers such as car evaporator having brazed portions to assemble fins and pipes by soldering. This is because a pickling method of this invention enables the sufficient cleaning of deposits derived from solders to facilitate the chemical transformation treatment, contributing to the improvement of corrosion resistance of heat exchanger and prevention of stinks caused by white rust.
(8) A treatment method for making a heat exchanger hydrophilic comprising previously performing the pickling treatment for a heat exchanger by any of methods according to the aforementioned (1)xcx9c(5), and performing a chemical transformation treatment to form a chemical conversion coating film by the chromium chromate treatment agent or chromium phosphate treatment agent, followed by the treatment for making the heat exchanger hydrophilic using the following treatment agent for hydrophilicity, so that the amount of coating film becomes 0.1xcx9c3 g/m2.
xe2x80x9cTreatment agent for hydrophilicityxe2x80x9d means a treatment agent which contains silica particulates and polymers of vinyl alcohol series in the weight ratio of 30:70xcx9c70:30 in aqueous medium, amounting to 0.2xcx9c25 weight percent in total for both, in which said silica particulates are coated with said polymer of vinyl alcohol series, and dispersed in the aqueous medium as coated particles having the average particle diameter 5xcx9c1000 nm.
(9) A treatment method for making a heat exchanger hydrophilic comprising previously performing the pickling treatment for a heat exchanger by any of methods according to the aforementioned (2)xcx9c(5), and performing a chemical transformation treatment to form a chemical conversion coating film by a zirconium series treatment, followed by the treatment for making said heat exchanger hydrophilic using the following treatment agent for hydrophilicity, so that the amount of coating film becomes 0.1xcx9c3 g/m2.
xe2x80x9cTreatment agent for hydrophilicityxe2x80x9d means a treatment agent which contains silica particulates and polymers of vinyl alcohol series in the weight ratio in the range 30:70xcx9c70:30 in aqueous medium, amounting to 0.2xcx9c25 weight percent in total for both, in which said silica particulates are coated with said polymer of vinyl alcohol series, and dispersed in the aqueous medium as coated particles having the average particle diameter 5xcx9c1000 nm.
As the chemical transformation treatment agent, the conventionally known chromium chromate treatment, chromate phosphate treatment, or non-chromium zirconium series treatment can be used.
The chromium chromate treatment agent is an aqueous solution containing chromic acid, fluoride and strong acid, including the reaction type chromate and electrolyte type chromate with the trivalent chromium as the principal ingredient, and a spreading type chromate in which hexavalent and trivalent chromium are mixed. On the other hand, the chromate phosphate treatment agent is a mixed aqueous solution containing chromic acid, orthophosphate and fluoride. For the chemical transformation treatment carried out with these chromate treatments, it is required to control each of the amounts of hexavalent chromium, phosphate ion and fluoride ion.
An example of the non-chromium ziruconium series treatment agent can be exemplified by ziruconium salts including zirconium fluoride. Furthermore, it is also preferred to add acids such as phosphoric acid, manganic acid, permanganic acid, vanadic acid, tungstic acid, molybdic acid, etc. to these salts. In addition, in the case of the use of non-chromium zirconium series treatment agents, it is essential to perform the washing treatment with pickling agent containing iron salts.
By performing the chemical transformation treatment with the above-described chemical transformation agent, chemical transformation film such as chromate coating film, chromium phosphate coating film, or zirconium series coating film containing no chromium are formed on the surface of heat exchanger.
A treatment agent for making the heat exchanger hydrophilic used in this invention comprising silica particulates coated with a polymer of vinyl alcohol series dispersed in aqueous medium is morphologically different from the mixture of silica particulates and resin particles, or silica particulates bound to resin with a silane compound in the conventional arts.
Silica particulates usable as the raw material of treatment agents to make a heat exchanger hydrophilic according to this invention can be exemplified by humed silica and colloidal silica. Among them, humed silica is prepared by hydrolyzing halosilane such as trichlorosilane and tetrachlorosilane at high temperature in the vapor phase, which is particulate having large surface area. Colloidal silica is a silica sol of the acid- or alkali-stable type dispersed in water. Particle diameter of silica particulates is 5xcx9c100 nm, preferably 7xcx9c60 nm on the average. When this average particle diameter is less than 5 nm, the irregularity of treated coating film is not sufficient, resulting in the decrease in hydrophilicity, and when it exceeds 100 nm, aggregates of large particle diameter are formed in the preparation of treatment agents, aggravating the painting processability.
A typical polymer of vinyl alcohol series usable in this invention is polyvinyl alcohol (PVA) obtained by saponifying a vinyl acetate polymer. PVA with a high saponification level is preferred, especially the one with a saponification level exceeding 98% is preferred. Denatured PVAs, for example, PVAs denatured with a carboxylic acid, silicon, amine and thiol can be also used as the polymer of vinyl alcohol series according to this invention. Furthermore, as the occasion demands, other hydrophilic polymers such as hydroxyl group-containing acrylic resins, polyacrylic acid, polyvinyl sulfonic acid, polyvinylimidazole, polyethylene oxide, polyamide, water-soluble nylon, etc. can be used together with PVA in amount of less than 50 weight percent relative to PVA.
Total content of silica particulates and polymer of vinyl alcohol series is 0.2xcx9c25 weight percent, preferably 1xcx9c5 weight percent Weight ratio of silica particulates to polymer of vinyl alcohol series is in the range 30:70xcx9c70:30, preferably 40:60xcx9c60:40.
When the aforementioned total content of vinyl alcohol polymer and silica particulate is less than 0.2 weight percent, effects of lasting hydrophylicity and deodorizer are not expressed, and, on the other hand, when said total content exceeds 25 weight percent, viscosity of the treatment agent becomes high, aggravating the painting processability. When the weight ratio of silica particulates to polymer of vinyl alcohol series is out of the range 30:70xcx9c70:30, with a higher ratio of silica particulates, the coating film formation becomes insufficient, resulting in the exfoliation of the film to emit dust smell from silica and base material, and with a higher ratio of polymer of vinyl alcohol series, hydrophilicity is reduced.
Amount of coating film formed by the treatment for making the metal surface hydrophilic is set up to be 0.1xcx9c3 g/m2, preferably 0.2xcx9c1 g/m2. When the coating film amount is less than 0.1 g/m2, the hydrophilic property is not expressed, and, on the other hand, when it exceeds 3 g/m2, the productivity is reduced.
(10) The treatment method for making a heat exchanger hydrophilic according to the aforementioned (8) or (9), wherein said treatment agent for hydrophylicity contains a deodorizer comprising an organic material having amido and/or phenol groups.
And, the deodorizer usable in this invention can be exemplified by organic compounds containing amido group and/or phenol group such as water-soluble polyamides, flavonoids, aqueous phenols, hydrazine derivatives (for example, carbodihydrazides, hydrazine adipate, hydrazine sebatate, hydrazine didodecate, hydrazine isophthalate, 1,6-hexamethylenebis(N,Nxe2x80x2-dimethylsemicarbazide), 1,1,1xe2x80x2,1xe2x80x2-tetramethyl-4,4xe2x80x2(methylene-di-p-phenylene)di-semicarbazide, etc.
(11) The treatment method for making a heat exchanger hydrophilic according to any of the aforementioned (8)xcx9c(10), wherein said treatment agent for hydrophilicity contains an antimicrobial drug.
The aforementioned treatment agent for hydrophilicity can be added with an antimicrobial drug besides deodorizer. Antimicrobial drugs usable in this invention can be exemplified by, for example, zink pyrithione, 2-(4-thiazoryl)-benzimidazole, 1,2-benzisothiazoline, 2-n-octyl-4-isothiazoline-3-on, N-(fluorodichloromethylthio)phthalimide, N,N-dimethyl-Nxe2x80x2-phenole-Nxe2x80x2-fluorodichloromethylthio)-sulfamide, methyl 2-benzimidazolecarbamate, bis(dimethylthiocarbamoyl)-disulfide,N-(trichloromethylthio)-4-cyclohexane-1,2-dicrboxyimide, and barium metaborate. These antimicrobial drugs can be used as the antifungal substance, antiseptic and antibacterial drug. Antimicrobial drugs can manifest their effects by adding them at the concentration higher than 10 ppm relative to the treatment agent for hydrophilicity.
(12) The treatment method for making a heat exchanger hydrophilic according to any of the aforementioned (8)xcx9c(11), wherein said heat exchanger is a car evaporator.
Herein, the following things are also included in this invention.
(13) A heat exchanger treated for making it hydrophilic by the treatment method for making a heat exchanger hydrophilic according to any of the aforementioned (8)xcx9c(12).
Another aspect of this invention may be described as follows.
(14) A pickling agent for a heat exchanger, which is used to perform a cleaning treatment to a heat exchanger made of aluminum materials prior to the performance of a chemical transformation treatment, containing at least one acid selected from a group comprising nitric acid, sulfuric acid and hydrofluoric acid.
(15) The pickling agent according to the aforementioned (14) which contains iron salt.
(16) The pickling agent according to the aforementioned (15), wherein said iron salt is iron sulfate, iron nitrate, iron acetate, or iron chloride.
(17) The pickling agent according to the aforementioned (15) or (16), wherein the content of said iron salt is in the range 0.01xcx9c5 weight percent.
The treatment method for hydrophilicity of this invention will be described below in detail.
 less than Cleaning Treatment greater than 
First, the cleaning treatment for heat exchanger is performed using a pickling agent. For cleaning a heat exchanger, it is sprayed with said cleaner, or soaked into a bath containing said cleaner. After the cleaning, the evaporator is washed with water, and then subjected to the chemical transformation treatment.
 less than Chemical Transformation Treatment greater than 
There is no particular limitation to this treatment, which can be performed, for example, by the immersion method, spraying method. etc. However, in the case of the chemical transformation treatment for a heat exchanger having a complex shape such car evaporator, etc., it is preferable to use the immersion method.
Treatment temperature is preferably the room temperature or slightly warmer temperature than that, in the range 10xcx9c70xc2x0 C., and the treatment time is preferably 3 sxcx9c5 min. Amount of the chemical conversion coating film is preferably 10xcx9c300 mg/m2 as the amount of each element (Cr, Zr) adhered to the metal surface.
When the amount of said chemical conversion coating film is less than 10 mg/m2, the anti-rust capability is often insufficient, and when it exceeds 300 mg/m2, it becomes uneconomical. After the chemical transformation treatment, washing with water is performed as the occasion demands, prior to the subsequent treatment for making it hydrophilic.
In addition, like the aforementioned treatment agent of zirconium series, titanium salts including titanium fluoride can be used as the non-chromium chemical transformation treatment agent. And, as an anti-rust treatment as effective as the chemical transformation treatment, the undercoating as the anti-rust treatment with resin primers may be performed. By performing the undercoating as the anti-rust treatment with said resin primers, the undercoating film by resin is formed on the surface of heat exchanger.
The aforementioned resin primer can be exemplified by water-soluble or water-dispersible aqueous resin, specifically, aqueous polymer compounds having carboxyl group or hydroxyl group such as poly (meta) acrylic acid, polyvinyl alcohol, carboxymethyl cellulose, etc., aqueous phenolic resin, aqueous polyester resin, aqueous epoxy resin, aqueous polyurethane, aqueous amino resin, etc.
Corrosion resistance of coating film can be improved by supplementing the aforementioned resin primers with metallic compounds such as zirconium compounds, etc. including fluorozirconic acid, fluorozirconium ammonium, etc. at the concentration of 100xcx9c10000 ppm.
After similarly treated as chemical conversion coating film, it is preferable to bake resin primers at 100xcx9c220xc2x0 C., preferably at 150xcx9c200xc2x0 C. for 10xcx9c60 min to make the dried coating film 0.1xcx9c10 xcexcm thick. When the baking temperature of resin primer is less than 100xc2x0 C., the film formation becomes insufficient, and when said temperature exceeds 220xc2x0 C., the lasting hydrophylicity is reduced. When the resin primer coating film is less than 0.1 xcexcm thick, the rust preventive capacity is often insufficient, and when said film exceeds 10 xcexcm thick, it becomes uneconomical.
 less than Treatment for Hydrophylicity greater than 
To prepare a treatment agent for hydrophilicity used in this invention, first, polymer of vinyl alcohol series (and other hydrophilic polymer, when the occasion demands. Hereafter simply referred to as polymer of vinyl alcohol series.) is dissolved or dispersed to make the concentration 0.3xcx9c17.5 weight percent, preferably 0.5xcx9c5 weight percent relative to the entire treatment agent. To this mixture were added silica particulates of 5xcx9c100 nm, preferably 7xcx9c60 nm in the average particle diameter to the final concentration 0.3xcx9c17.5 weight percent, preferably 0.5xcx9c5 weight percent relative to the entire treatment agent.
Alternatively, by dispersing silica particulates in an aqueous solution of polymer of vinyl alcohol series containing 5xcx9c50 weight percent relative to silica particulates as its solid, said silica particulates are previously coated with polymer of vinyl alcohol series, and then the concentration may be adjusted by adding an aqueous solution of polymer of vinyl alcohol series.
When polymer of vinyl alcohol series is mixed with silica particulates as described above, aggregation occurs by the interaction between them. Therefore, these aggregates are forcibly dispersed using ultrasonic disintegrator or micromedium disperser, etc.
Since disperser such as mixer used for simple stirring and dispersion cannot disperse aggregates, it is necessary to use a device having the grinding function like a mill or vigorous stirring effects on minute parts like the ultrasonic wave. As examples for such disperser, there are an ultrasonic homogenizer (US series) from Nippon Seiki Seisakusho, and a super mill (HM-15) of Inoue Seisakusho. Aggregates thus forcibly dispersed become particles of 5xcx9c1000 nm in the average particle diameter comprising silica particulates the surface of which is coated with polymer of vinyl alcohol series, and stabilized as dispersion in aqueous medium.
In the aforementioned treatment agents for hydrophilicity, various additives can be supplemented besides the aforementioned deodorizer and antimicrobial drugs as the occasion demands. These additives can be exemplified by lubricant, surfactant, pigment, dye and inhibitor to prevent corrosion.
In this invention, the treatment for hydrophilicity is performed using the treatment agent for hydrophilicity thus prepared as described above. There is no particular limitation in the treatment method, and treatment can be carried out, for example, by immersion method, spraying method, etc. However, in the case of the treatment for a heat exchanger having a complex shape such a car evaporator, etc., it is preferable to use the immersion method. Preferable temperature of the treatment liquid is around 10xcx9c50xc2x0 C., and treatment time is 3 sxcx9c5 min.
After the treatment for hydrophilicity, the hydrophilic coating film can be obtained by baking the treated surface at 100xcx9c220xc2x0 C., preferably 150xcx9c200xc2x0 C. for 10xcx9c60 min. When the baking temperature is less than 100xc2x0 C., film formation becomes insufficient, and, on the other hand, when it exceeds 220xc2x0 C., the lasting hydrophylicity is reduced.
Heat exchanger treated for hydrophilicy of this invention (heat exchanger made hydrophilic) is manufactured by the aforementioned method, and a chemical conversion coating film is formed on the surface of aluminum material which has been treated by the acid washing with a pickling agent, furthermore, on said surface, the hydrophilic coating film is formed in amount of 0.1xcx9c3 g/m2. This hydrophilic coating film is formed from a treatment agent for hydrophilicity containing silica particulates coated with a polymer of vinyl alcohol series.